Production of substituted derivatives of n, n&#39;-methylenebis-(hexahydropyrimidines)



UNITED STATES ATENT OFFICE PRODUCTION OF SUBSTITUTED DERIVA- TIVES OFN,N-METHYLENEBIS- (HEXAHY- DROPYRIMIDINES Glen H. Morey, Terre Haute,Ind, assignor to Commercial Solvents Corporation, Terre Haute,

Ind., a corporation of Maryland.

N Drawing. Application August 28,v 1948, Serial N 0. 46,724

7 Claims. (01. 260251) My invention relates to theproduction of substituted derivatives of N,N-methylenebis-(hexahydropyrimidines). Moreparticularly, it relates to compounds of the following structuralformula 2 tion or react with any products thereof may be employed.

The diamines used in my process include N-isopropyl-1,3-propanediamine,N-(3 dibutylaminoand to a method of preparing them: 5 propyl)-1,3-propanediamine,. N-(2 ethylhexyl) H H H H 1,3 -propanediamine, N-(beta-hydroxyethyl) -1,3 propanediamine, N cyclohexyl-l,3propanediamine, N-furyl-1,3-propanediamine, N-phenyll=,3- H-C 0-H H-CC-H propanediamine, N-(-2 phenylethyl) 1,3 pro- 1 1Q panediamine, andthe like.

l In order to obtain thesubstituted derivatives ofN,N-methylenebis-(hexahydropyrimidines) of H V H D H my invention it isnecessary that one of the amino wherein R representsa substituentselected from ps of dia e p y in the r t on the group consisting ofalkyl, cycloalkyLdialkylbe p ma y a d the oth r s a y. f t

aminoalkyl, furfuryl, aryl, aralkyl, hydroxyalkyl and alkoxyalkyl.

As examples of the new compounds included in the above formula maybementioned: N ,N-methylenebis-(-3 isopropyl hexahydropyrimidine) N,Nmethylenebis [-3-(-3 dibutylaminopropyl) -hexahydropyrimidine], N,N'-methylenebis- 3 cyclohexylhexahydropyrimidine), N,N.- methylenebis 3furfurylhexahydropyrimidine) N ,N-methylenebis--3-phenylhexahydropyrimidine) N,N -methy1enebis--3-benzylhexahydropyrimidine), N,N-methylenebis 3 2hydroxyethyl)hexahydropyrimidine], N,N- methylenebis--3-methoxyethylhexahydropyrimidine).

Compounds of the above character may be produced by reacting at least1.5 moles, and preferably about two moles, of formaldehyde with adiamine of the following general structure until amino groups areprimary, resinous, tarry materials are formed. Contrary to what onemight expect, the primary amino groupsof the diamines used in myinvention do not form resinous or tarry products. 7

These neW products producedby my novel reaction may be used variously.One use is in the production of'wetting agents by converting them to thelauric or oleic salts, or to quaternary ammonium salt. The reactionproducts of formaldehyde may be used as a source of plastics, forexample in condensation reaction with phenol.

The following examples illustrate the process by which my new compoundsmay be prepared.

Example I A solution of 152 grams (1.31 moles) ofN-isopropyl-1,3-propanediamine in 100 cc. of methanol was firstprepared. To this was then added condensation is substantially complete:portionwise 84 grams (2.8 moles) of formaldehyde H H in 40% aqueoussolution while stirring and cool- I l ing to maintain the temperature at30-40 C. The

I E solution was finally heated to 60 C. on the steam H H H H bath. Themethanol and other volatile constituwherein R represents thesubstituents described above.

The reaction between formaldehyde and the amine is preferably carriedout at a temperature below about 125 C. The reaction is exothermic incharacter and in general is initiated at a temperature within the rangeof 2550 C. It is frequently desirable or even necessary to cool thereaction mixture in order to maintain it Within the generally preferredrange of 40-90 C.

A solvent which is inert under the conditions of the reaction may beused for maintaining the reactants in solution while the reaction isbeing carried out. Examples of suitable solvents include methanol andother monohydric alcohols. In general, solvents which do not enter intothe reacents were distilled off at 50 mm. mercury pressure, to a pottemperature of C. The product was then distilled at 2 mm. pressure andyielded 91 grams of N ,N -methylenebis-(-3-isopropyl-1,3-diazacyclohexyl) boiling at 135 C.

Example II One mole, 2&3 grams, ofN-(-3-dibutylaminopropyl)-1,3-propanediamine was placed in a beaker with200 cc. of methanol. Then two moles of formaldehyde in 40% aqueoussolution were added portionwise While stirring and cooling to maintainthe temperature at 40-50 C. After about three-fourths of theformaldehyde had been added, two layers formed. The mixture Was finallyheated and stirred for a few minutes on 3 the steam bath. The methanoland other volatile constituents were then distilled ofi to a pottemperature of 130 C. A small amount of additional material wasdistilled off at 2 mm. pressure to a pot temperature of 150 C. Theundistilled material left in the flask consisted of 230 grams ofN,N'-methy1enebis-[-3-(-3 dibutylaminopropyl) -l,3-diazacyclohexyl] Iclaim as my invention:

1. As a new composition of matter, a substituted derivative ofN,N'-methylenebis-(hexahydropyrimidines) 2. As a new composition ofmatter, a substituted derivative ofN,N'-methylenebis-(hexahydropyrimidines) having the structure:

wherein R represents a substituent selected from the group consisting ofalkyl, cycloalkyl, dialkylaminoalkyl, furfuryl, aryl, aralkyl,hydroxyalkyl and alkoxyalkyl.

3. As a new composition of matter, N,N'-methylenebis-(-3-isopropyl-1,3-diazacyclohexyl) 4. As a new composition of matter,N,N-methylenebis 3 (-B-dibutylaminopropyl) -l,3-diazacyclohexyl] 5. Aprocess for preparing substituted derivatives ofN,N-methylenebis-(hexahydropyrimiwherein R represents a substituentselected from the group consisting of alkyl, cycloalkyl, dialkylwhereinR represents a substituent selected from the group consisting of alkyl,cycloalkyl, dialkylaminoalkyl, furfuryl, aryl, aralkyl, hydroxyalkyl andalkoxyalkyl, said process comprising mixing formaldehyde with a diaminehaving the formula:

wherein R is a radical selected from the group consisting of alkyl,cycloalkyl, aryl, and aralkyl radicals, in the proportion of at least1.5 moles of formaldehyde per mole of diamine.

'7. The process of claim 6 wherein R is an isopropyl group.

GLEN H. MOREY.

No references cited.

Certificate of Correction Patent No. 2,527,323 October 24, 1950 GLEN H.MOREY 7 It is hereby certified that error appears in the printedspecification of the above numbered patent requiring correction asfollows:

Column 1, lines 12 to 14, inclusive, for that portion of the formulareading 0 c read and that the said Letters Patent should be read ascorrected above, so that the same may conform to the record of the casein the Patent Ofiice. Signed and sealed this 2nd day of January, A. D.1951.

THOMAS F. MURPHY,

Assistant Uommz'ssz'oner of Patents.

1. AS A NEW COMPOSITION OF MATTER, A SUBSTITUTED DERIVATIVE OFN,N''-METHYLENEBIS-(HEXAHYDROPYRIMIDINES).